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Cationically-charged particulates and compositions containing the
cationically-charged particulates for application to keratinous materials
are provided. Methods of preparing the cationically-charged particulates
are also disclosed.

Inventors:

Lee; Wilson A.; (Hauppauge, NY)

Applicant:

Name

City

State

Country

Type

ELC MANAGEMENT LLC

Melville

NY

US

Family ID:

1000002279665

Appl. No.:

15/354793

Filed:

November 17, 2016

Related U.S. Patent Documents

Application Number

Filing Date

Patent Number

62256292

Nov 17, 2015

Current U.S. Class:

1/1

Current CPC Class:

A61Q 1/10 20130101; A61K 8/817 20130101

International Class:

A61K 8/81 20060101 A61K008/81; A61Q 1/10 20060101 A61Q001/10

Claims

1. A method of treating particulates comprising: encapsulating each
particulate in a first, inner coating comprising a cationically-charged
material in an amount sufficient to impart a cationic charge in the range
of from about 0.1 mV to about 400 mV to the particulates.

2. The method of claim 1, which comprises introducing the particulates to
a microfluidizer and subjecting the particulates to at least one spray
coating operation with a first composition comprising a water-soluble or
water-dispersible cationically-charged material, followed by at least one
drying step.

3. The method of claim 2, wherein a weight ratio of the first composition
to the particulates is in the range of from about 0.1:1 to about 5:1.

4. The method of claim 3, wherein the weight ratio of the first
composition to the particulates is in the range of from about 0.1:1 to
about 2:1.

5. The method of claim 1, comprising: encapsulating each of the
cationically-charged particulates in a second, outer coating comprising a
film former material in an amount sufficient to render the
cationically-charged particulates hydrophobic.

6. The method of claim 5, wherein encapsulating each of the
cationically-charged particulates in the second, outer coating comprises
subjecting the cationically-charged particulates to at least one spray
coating operation with a second composition comprising a film former
material, followed by at least one drying step.

7. The method of claim 6, wherein a weight ratio of the second
composition to the cationically-charged particulates is in the range of
from about 0.1:1 to about 60:1.

8. The method of claim 7, wherein the weight ratio of the second
composition to the cationically-charged particulates is in the range of
from about 0.1:1 to about 30:1.

9. The method of claim 2, wherein the cationically-charged particulates
are subjected to at least one further spray coating operation with a
composition comprising at least one of a water-soluble or
water-dispersible cationically-charged material, a water-soluble or
water-dispersible anionically-charged material or both, wherein the at
least one further spray coating operation is followed by at least one
drying operation.

10. The method of claim 6, wherein prior to encapsulating the
cationically-charged particulates with the second, outer coating, the
cationically-charged particulates are subjected to at least one further
spray coating operation with a composition comprising at least one of a
water-soluble or water-dispersible cationically charged material, a
water-soluble or water-dispersible anionically charged material or both,
wherein the at least one further spray coating operation is followed by
at least one drying operation.

11. The method of claim 1, wherein the cationically-charged material
comprises a naturally-derived or a synthetic cationic polymer.

12. The method of claim 11, wherein the naturally-derived cationic
polymer comprises a cationically charge-modified derivative of at least
one of guar gum, cellulose, a protein, a polypeptide, chitosan, lanolin,
or a starch.

16. The method of claim 5, wherein the film former material comprises a
silicone, an acrylates polymer, an acrylates copolymer, a
polyvinylpyrrolidone (PVP) derivative, a polyurethane, a polyvinyl amine,
a polyvinyl acetate, sucrose acetate isobutyrate, or a combination of any
two or more thereof.

17. The method of claim 16, wherein the film former material comprises
dimethicone and trimethylsiloxy silicate; dimethicone,
trimethylsiloxysilicate and polyglyceryl-3 disiloxane dimethicone; or
polyurethane.

18. The method of claim 1, wherein the particulates are in the form of
synthetic powder particulates, synthetic fibers, or a combination
thereof.

19. The method of claim 18, wherein the particulates are derived from
nylon, polypropylene, or a combination thereof.

20. The method of claim 18, wherein the particulates are in the form of
fibers having a length in the range of from about 1 micrometer to about 4
millimeters and a weight in the range of from about 3 to about 20 denier.

21. The method of claim 20, wherein the fibers have a length in the range
of from about 1 to 2 millimeters and a weight in the range of from about
5 to about 10 denier.

22. The method of claim 18, wherein the fibers have a cross-sectional
shape which is round, oval, triangular, hexagonal, heart-shaped,
star-shaped, or a combination of any two or more thereof.

23. A treated particulate produced by the method of claim 1.

24. A treated particulate produced by the method of claim 5.

25. A treated particulate having a first, inner coating comprising
polyquaternium-6 and a second, outer hydrophobic coating comprising
silicone or polyurethane, the treated particulate having a cationic
charge in the range of from about 0.1 mV to about 400 mV.

Description

FIELD OF THE INVENTION

[0001] The invention relates to novel cosmetic compositions suitable for
application to keratinous materials, such as eyelashes, eyebrows and
hair, and to methods of making the compositions. More specifically, the
invention relates to fibers or other particulates which have been
uniformly coated with a cationically-charged material, and to
compositions containing the coated particulates.

BACKGROUND OF THE INVENTION

[0002] Consumers desiring longer and thicker eyelashes have traditionally
resorted to the use of false eyelashes which are applied with glue to
natural eyelashes or to costly lash extensions. As an alternative,
various mascara products have been popular. Nevertheless, some eyelashes
are just too sparse for just any type of volumizing mascara to make them
look more dramatic. On the other hand, even women with a great eyelash
fringe may desire a more intense result than may be achieved using their
favorite mascara. Features that mascara products are expected to have
include the ability to darken, thicken and lengthen the eyelashes so as
to achieve eyelashes having a fuller appearance without clumping or
flaking off. In addition, it is desirable that the product be water-
and/or smudge-resistant yet not be difficult to remove, The cosmetic
industry has responded to this demand by providing mascara compositions
containing fibers, waxes, and/or bulking or filler agents; however, there
are limitations on the amount of such ingredients which can be added to
the formulations without reducing processibility of the formula, or
interfering both with loading a brush with product and delivering product
from the brush to the eyelashes. Also commercially available are fibers
for application to mascara-coated eyelashes. A disadvantage associated
with such fibers is that when drawn out of a receptacle, the fibers tend
to pick up negative charges from the atmosphere which causes them to
become statically-charged and to repel one another and fly about. To deal
with this issue, fibers have also been formulated into gel products.
Nevertheless, fibers in such products often do not sufficiently adhere to
the eyelashes upon application or even after dry down but tend to flake
off onto the face and into the eyes causing irritation.

[0003] There continues to be a need to formulate a fiber-containing
composition which will better adhere to the eyelashes, eyebrows or hair
to achieve the desired improvements in volume and/or length, and without
the aforementioned disadvantages associated with conventional products.

SUMMARY OF THE INVENTION

[0004] The present invention relates to canonically-charged particulates,
and to compositions comprising the cationically-charged particulates, for
application to negatively charged keratinous materials, such as
eyelashes, eyebrows and hair. The particulates are provided with the
cationic charge by encapsulation with a coating comprising a
cationically-charged material. The cationically-charged particulates are
optionally coated with a film-former finish material to further seal the
canonically-charged coating to the particulates and to render the
particulates hydrophobic. The film-former material may be hydrophilic or
hydrophobic, but is hydrophobic on dry-down, The invention also relates
to methods of preparing the cationically-charged particulates and
particulate-containing cosmetic compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

[0005] FIG. 1 depicts a sheet of paper onto which statically-charged
fibers have scattered from a brush withdrawn from a vial of the virgin
fibers.

[0006] FIG. 2 depicts a blank sheet of paper onto which film-former
coated, cationically-charged fibers have not been released from a brush
withdrawn from a vial of the charged fibers.

[0007] FIG. 3 is a photograph showing the scattering of statically-charged
fibers under the right eye after the in the range of from about 0.1 mV to
about 400 mV fibers were applied to mascara-coated eyelashes, and further
showing no scattering of film-former coated, cationically-charged fibers
under the left eye after the film-former coated, cationically-charged
fibers were applied to mascara-coated eyelashes.

[0008] FIG. 4 is a photograph of the right eye area taken one hour after
the initial application of statically-charged fibers to mascara-coated
eyelashes followed by wiping the undereye are clean of fallen fibers.

[0009] FIG. 5 is a photograph of the left eye area taken one hour after
the initial application of film-former coated, cationically-charged
fibers to mascara-coated eyelashes followed by wiping the undereye area
clean.

DETAILED DESCRIPTION OF THE INVENTION

[0010] The use of coatings on the surfaces of particles has been known for
more than forty years in the personal care industry. Such coatings are
widely used to encapsulate tablets so that they are completely and evenly
coated with a coating material. The benefits of a coated tablet include
the ability, upon degradation of the coating, to absorb materials from an
environment; or to release materials, such as active agents disposed in a
matrix of the coating, into an environment. As coatings may possess
porosity, as in the case of a zeolite, such coating do not require
release in order to render absorption or release of a material into or
out of the matrix of the coating. In cases such as these, very high
selectivity may be obtained by using properly tuned pore characteristics.

[0011] The surface treatment of pigments has also been used to improve the
ability of incorporating them into cosmetic formulations. For example,
pigments coated with different types of silicones are commercially
available and when used as cosmetic pigments in formulations the coating
facilitates the incorporation of the pigment into hydrophobic
formulations whereas the untreated pigment would generally remain poorly
dispersed. Other pigments may be coated with fluorocarbon polymers to
improve their adhesive power while also forming a film upon application.
Still other pigments may coated with natural polymers such as proteins,
for example collagen. These types of coatings do not demonstrate a
waterproofing property but the natural proteins do enhance ease of
pigment dispersion into the hydrophilic phase of the cosmetic formulation
and may be used to introduce a cationic charges into the formulations.
Although protein-coated pigment introduced into the hydrophilic phase
demonstrates better binding on dry down, such coated pigments have not
been shown to adhere sufficiently to skin. Additionally, dispersed
proteins tends to separate out from such formulations during
manufacturing.

[0012] A commonly used material for an encapsulation coating is silicone
polymer. There have been many efforts to improve the adhesion of
particulates to keratinous materials by coating the particulates with
silicones. Silicone polymers have been widely used because they possess
two advantageous properties: biocompatibility and permeability to gases
and small molecules. Advantages for use in cosmetics include their
contribution to waterproofing or water-resistance propel ty, feel, and
shine, and they also are compatible with most oil phases of a base
formulation. Nevertheless, the use of silicones for coating particulates
has its drawbacks, including excessive shine and incompatibility with
water and water-soluble ingredients.

[0013] Nevertheless, prior to the present invention. it had not been known
to coat particulates with a cationically-charged material for formulation
into cosmetic compositions for application to keratinous materials. Dry.
treated particulates of the invention demonstrate greater adhesion to
negatively-charged eyelashes, eyebrows and hair compared with untreated
particulates. The dry, treated particulates may also be incorporated into
volumizing mascara, eyebrow filler and hair filler formulations to
provide such formulations with superior adhesion to negatively charged
eyelashes, eyebrows and hair.

[0014] Keratinous materials have an anionic charge of about -24 mV. The
surface of particulates, for example, fibers, treated according to the
present invention, will typically have a net cationic charge in the range
of from about 0.1 mV to about 400 mV which will facilitate their
adherence to the keratinous materials. A net cationic charge of greater
than about 400 mV would be expected to create dramatic flyaway of the
fibers (due to repellent forces between fibers) when pulling a brush
loaded with dry, treated particulates out of a container holding the dry
treated particulates. When incorporated into a base formulation, treated
particulates having a net cationic charge of greater than about 400 mV
would tend to be tacky and agglomerate in the container. Particulates
with a net cationic charge of less than about 0.1 mV would not be
expected to adhere sufficiently to eyelashes, eyebrows and/or hair,
whether the particulates are used dry or incorporated into a base
formulation.

[0015] In accordance with compositions and methods of the present
invention, the dry, treated particulates have a net cationic charge,
measured as the zeta potential, in the range of from about 0.1 mV to
about 400 mV, such as from about 24 mV to about 200 mV, for example, in
the range of from about 60 mV to about 150 mV.

[0016] The cationic charge is imparted to the particulates by means of at
least one coating containing a cationically-charged material. In some
embodiments of the present invention, the coating comprises a natural or
synthetic cationic compound dispersed in an aqueous-based medium,
preferably a water and alcohol medium, to facilitate evaporation of the
medium and drying of the particulates. One class of such compounds
includes cationically charge-modified polymers where the cationic groups
enhance the polymer's substantivity to anionic substrates, such as
keratinous materials. Natural cationically charge-modified polymers may
be derived from various animal and plant sources including guar gum,
cellulose, proteins, polypeptides, chitosan, lanolin, and starches and
combinations thereof. Synthetic compounds include those with quaternary
ammonium functional groups, for example, cationic polymers, such as
polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-10,
polyquaternium-39, polyquaternium-44, polyquaternium-46, quaternary
ammonium salts, including, distearyldimonium chloride,
cinnamidopropyltrimonium chloride, cetrimonium chloride, and guar
hydroxypropyltrimonium chloride, and combinations of any two or more
cationically-charged materials. A cationic coating comprising
polyquaternium-6 is particularly preferred for its charge density. A
further example of a cationically-charged coating useful in the present
invention is powdered iron (FeO).

[0017] Particulates coated with the cationically-charged coating may
optionally, but not necessarily, be further encapsulated with a
film-former finish. The film former aids in the adhesion of the
cationically-charged material to the particulate surfaces, and
additionally can be configured to impart hydrophobicity to the
particulate surfaces. So as not to hinder the film former from binding to
the cationically-charged surfaces of the particulates, the
cationically-charged coating typically comprises water in an amount of
between about 0.01 and 5.00 percent by weight after drying which limits
their charge density.

[0018] The film former coating preferably comprises at least one
water-soluble or water-dispersible polymer having a surface tension of
less than about 75.gamma., and preferably in the range of from about
20.gamma. to about 65.gamma.. The polymers preferably exhibit good
water-resistance, adhesion and flexibility on dry down. Film forming
polymers useful for encapsulating the cationically coated particulates,
may be hydrophilic or hydrophobic, but are hydrophobic when dry. Examples
of suitable polymers, include, but are not limited to, silicones, such as
methyltrimethicone, trimethylsiloxysilicate, and dimethicone, dimethicone
and trimethylsiloxysilicate, and the like; acrylates polymers and
copolymers, such as Syntran PC 5775, Syntran PC 5776, Avalure AC-120,
Daitosol 5000AD, Daitosol 5000SJ; Daitosol U9-40, Vinylsol 214oL Vinylsol
1086 WP; polyvinylpyrrolidone (PVP) derivatives, such as PVP K-30, PVP/VA
E-635, PVP/VA W-735; polyurethanes, such as Luviset P.U.R., Giovarez
P-0580, and Baycusan C 1004; polyvinyl amines and polyvinyl acetates.
Non-polymeric film-former finishes may include, but are not limited to,
esters, such as sucrose acetate isobutyrate, which may be used alone, or
in combination with any of the aforementioned polymers.

[0019] In one preferred embodiment of the invention, the film-former
coating is a silicone polymer blend. A film former solution may contain,
for example, dimethicone and trimethylsiloxysiliate in trisiloxane. When
dried, this coating creates a high contact angle with the particulates
which renders the treated particulates particularly compatible with
water-in-oil and water-in-silicone systems. In another preferred
mbodiment, a film-former solution contains dimethicone,
trimethylsiloxysilicate and polyglyceryl-3 disiloxane dimethicone in
trisiloxane. When dried, this film former creates a lesser contact angles
with particulates. It possesses hydrophilic (i.e., polyglycerin) side
chains which enhance the compatibility of the treated particulates in
oil-in-water and silicone-in-water systems.

[0020] The amount of film former used should be an amount sufficient to
encapsulate the cationically charged particulates and render them
hydrophobic, but not be so great as to decrease the net cationic charge
of the particulates to a level which would reduce the level of cationic
charge below a value useful in the present invention. In the case where
the treated fibers or a formulation containing the treated fibers, are
used on the eyelashes, it is preferred that the cationically-charged
fibers be encapsulated in film former, since oil in the skin around the
eyes may dissolve the cationic material on the fibers. The dissolved
cationic material may make contact with and irritate the eyes. The film
former encapsulation is not necessary where the fibers or a formulation
containing the fibers will be used on the eyebrows or in the hair.

[0021] Additional coatings may be deposited on the particulates prior to
the final film former finish. Such additional coatings may be liquid or
solid, and may deposit anionic material, cationic material, or both. In
some embodiments of the invention, the additional coatings contain
proteins, peptides, or a combination thereof. An intervening anionic
coating may be used to balance a high cationic charge of particulates
coated with the initial cationically charged coating. The net cationic
charge may also be modified with the film former coating. A thicker the
film former coating may also be used to reduce a high cationic charge.
The coated particulates, however, carry a net final charge of from about
0.1 to about 400 mV so as to adhere satisfactorily to negatively charged
keratinous materials. One example of a natural intervening coating is an
aqueous-containing solution containing 0.1 wt. % grape seed extract. The
coating, when dried, carries a cationic charge.

[0022] Any of the coating compositions may contain compatible actives,
such as conditioning and/or rejuvenating ingredients. Benefits of
conditioning ingredients include added shine, but also flexibility and
moisture which, for example, when included in mascara, help keep
eyelashes, pliable and less likely to dry out and break. Conditioning
ingredients in mascara contribute to a more even mascara application,
since when eyelashes are conditioned, the surfaces are smoother. The
smoother surfaces help pigment in mascara to adhere more evenly to
eyelashes. Some of these conditioning agents may be moisturizers which
penetrate hairs along the lashline, making them softer. Other agents,
such as humectants, may attract moisture into the eyelashes. Still other
agents, for example, proteins or peptides, are said to make the eyelashes
stronger by reinforcing fibers that make up the hair strands.
Additionally, these proteins and/or peptides may help to plump the
eyelashes which is particularly beneficial to those with thin or sparse
eyelashes.

[0024] In addition to pigment, e.g. iron oxides, which may be contained in
or associated with, untreated particulates, pigment also may be trapped
in any of the coatings, that is, the initial cationic coating, the film
former finish, or any intervening coatings, to intensify color and
promote volume.

[0025] In accordance with the compositions and methods of the present
invention, particulates, such as fibers or powders, suitable for
treatment according to the present invention, may be made of various
materials, naturally-derived, semi-synthetic and/or synthetic. As
naturally-derived particulates, mention may be made of, for example,
cellulose, and cellulose-based materials, including, but not limited to,
cellulose (and) magnesium stearate, cotton, linen, and so forth. Also
useful is polylactic acid, a thermoplastic aliphatic polyester derived
from corn starch, tapioca or sugar cane. Also suitable as particulate
matter for use in the present invention would be a semi-synthetic
material such as rayon, a manufactured and regenerated cellulose fiber.
Synthetic particles may include, but are not limited to, those made from
nylon or polypropylene. Synthetic particulates are said to be
particularly useful for imparting volume and length to mascara and
eyebrow- and hair-filler products. Synthetic particulates may contain
pigments such as carbon black or iron oxides to enhance the overall color
effect of products in which they are incorporated.

[0026] Fibers useful in carrying out the invention may have a length in
the range of from about 1 micrometer to about 4 millimeters and a weight
in the range of from about 3 to about 20 denier. Preferably, the fibers
are from about 1 millimeter to about 4 millimeters in length, and have a
denier in the range of from about 3 to about 15. In certain preferred
embodiments of the invention, the fibers have a length in the range of
from about 1 millimeter to about 2 millimeters, and a denier in the range
of from about 5 to about 10. The fibers may take any cross-sectional
form, such as round, oval, triangular, hexagonal, heart-shaped,
star-shaped, and so forth.

[0027] One particularly preferred synthetic fiber is composed of nylon-6
(And) iron oxides (And) triethoxycaprylylsilane (And) silica, and is
available as NFBL-10D-1R-1MM from Kobo Products, Inc. These fibers are
black, have a round cross-section, a length of about 1 millimeter and a
denier of about 10. Another preferred synthetic fiber is SPLASH Fiber II
7T-1MM from Kobo Products, Inc. which is composed of nylon-6 (And) silica
(And) iron oxides. These fibers have a 7 decitex width (about 6.3
denier), a 1 millimeter length, are charcoal black in color, and have a
hexagonal cross-section resulting in a "flower" cross-sectional shape.
The greater surface area of these fibers, due to their shape, is also
said to offer a more volumizing effect to eyelashes to which the mascara
is applied than would typical fibers having a round to oval
cross-section, particularly by filling inbetween sparse lashes. Also
useful is FDA certified carbon black,10 denier, 1 mm round nylon fiber
(nylon-6 NFCB-10D-1R-1mm, available from Daito Kasei Kogyo Co. Ltd.).

[0028] In accordance with some embodiments of the invention, the
particulates are in the form of a fine powder which may take the form of
a flake-shaped or plate-like, cellulose product, the flakes having a
thickness of about 1 to 2 micrometers and a width of about 8.8
micrometers. Such a powder is available as silk cotton PW fibers, from
Kobo Products, Inc.

[0029] In some embodiments of the present invention, fibers having various
cross-sectional shapes, lengths and deniers may be blended, with or
without powders particulates, in compositions of the present invention to
achieve customized formulations for a desired effect; that is, enhanced
volume and/or length, when applied to keratinous materials.

[0030] In accordance with the present invention, a method of coating
particles comprises encapsulating the particles with at least one
cationically charged material, for example a cationic polymer, optionally
followed by coating with a water-soluble polymeric film finish coating to
further seal the cationically charged coating to the particle surfaces.
In some embodiments of the invention, the particulates are coated with
one or more additional coats of cationic or anionic material or a
combination thereof, the net cationic charge of the final dried
particulates falling within a range of from about 0.1 mV to about 400 mV.
One skilled in the art would appreciate that any method which will coat
the particulates may be used as long as the treated particulates retain a
net catonic charge in the range of from about 0.1 mV to about 400 mV.

[0031] One known method of coating or encapsulating particles, for
example, fibers, is spray coating. Fibers are introduced into a reactor
or microfluidizer which acts like a vortex. Air is pumped into a chamber
of the fluidizer from the bottom cauising the fibers to fly around. The
volume of air flow (i.e., flap) is controlled to prevent the light weight
fibers from clogging the fluidizer filter. Thereafter, a solution, a
dispersion, or an aqueous-containing emulsion, of a spray formulation
containing a cationically charged material is introduced into the
microfluidizer, and the circulating fibers are coated with the
cationically-charged solution. The spray composition is sprayed by one or
more nozzles situated in various regions of the microfluidizer. Typically
for each spraying operation, the pressure used may be in the range of
from about 1.5 to about 3.5 bar, such as about 2.5 bar, and the pump
speed will vary depending on the viscosity of the spray formulation. The
pump speed may be, for example, in the range of from about 2.5 to about
30 rpm, such as from about 5 to about 10 rpm. As an example of this type
of process, particles, such as fibers or powder particulates, to be
coated are stirred by a gas stream which also ensures their drying (i.e.,
the evaporation of the organic solvent and/or water). This method
involves at least one coating, but may include successive coatings, of
the fibers with the spray formulation, followed by at least one drying
operation to evaporate off the organic solvent and/or water.

[0032] The cationically-charged material covalently bonds to the surfaces
of naturally-derived particulates carrying surface hydroxyl groups, for
example, cellulose-based particulates. On the other hand, the
cationically-charged material does not bond to, but coats, synthetic
particulates.

[0033] Optionally, one or more additional spray formulations, for example,
a solution, a dispersion, or an emulsion, containing a film-former
material, may be introduced into the fluidizer while air is pumped into
the fluidizer chamber, so as to further coat the cationically-charged
fibers with the film-former finish material. The twice-coated fibers are
then dried again. The film former finish imparts hydrophobicity to the
treated fibers. In the case where naturally-derived particulates having
surface hydroxyl groups are used, it is particularly useful that the
cationically charged particulates receive a film former coating which
will render the particulates hydrophobic.

[0034] Optionally, one or more additional coatings containing cationic
and/or anionic material may be sprayed onto the particulates, prior to
the coating with film former, as long as the net final charge of the
particulates is cationic and is in the range of from about 0.1 mV to
about 400 mV. Each spraying step is followed by a drying step, prior to
the final coating with the film former material. The resulting
particulates are hydrophobic.

[0035] Using confocal microscopy, the inventors have determined ranges of
the weight of the coating materials to the weight of the particulates
useful in carrying out the spray coating operations. Various ranges were
tested, including 0.1:1, 0.25:1, 2.25:1, 3.75:1, 7.25:1, 10:1, 15:1 and
30:1. It was observed that, for use as dry, treated particulates intended
for direct application to keratinous material, a useful range of the
weight of the solution, dispersion, or emulsion containing the charged
coating material to the weight of the particulates in a spray coating
operation is in the range of from about 0.1:1 to about 2:1, such as about
0.25:1. A ratio of less than about 0.1:1 is considered undesirable, as
such lesser amount would not sufficiently encapsulate the particulates
(i.e., the cationic charge would be too low to be useful). The use of a
ratio of greater than about 2:1 is also considered undesirable as the
additional layers of solution, dispersion or emulsion containing the
charged coating material would result in flyaway of the particulates due
to the strong charges which begin to repel one another. In the case in
which the dried, treated particulates are incorporated into a cosmetic
base formula, such as a mascara composition, a broader useful range of
the weight of the solution, dispersion, or emulsion containing the
charged coating material to the weight of the particulates was observed;
the range being from about 0.1:1 to about 5:1, such as about 0.25:1. A
useful range of the weight of the solution, dispersion or emulsion
containing the film former to the cationically charged particulates is
from about 0.1:1 to about 30:1, such as about 3.75:1. A lesser amount of
the film former would not be expected to result in dried, sufficiently
coated cationically charged particulates. A greater amount of the film
former would be too viscous and may result in processing challenges,
including clogging the spray apparatus of the microfluidizer. In the case
in which the dried, treated particulates are incorporated into a cosmetic
base formula, such as a mascara composition, a broader useful range of
the weight of the solution, dispersion, or emulsion containing the film
former material was observed; the range being about 0.1:1 to about 60:1,
such as from about 0.1:1 to about 30:1, for example, about 3.75:1. A
lower amount of film former would not be expected to provide sufficient
coating to seal the prior coats onto the particulate surfaces and to
impart hydrophobicity to the particulates. A greater amount of film
former would result in overly tacky particulates which would be expected
to agglomerate in the base formula.

[0036] Dry, treated particles according to the present invention may be
provided in a receptacle including a cap fitted with an applicator of any
type, such as a molded or a twisted wire brush, which would be suitable
for loading product as it is withdrawn from the receptacle and for
depositing the particles on a keratinous surface, including eyelashes,
eyebrows or hair. The dry, treated particles may be encapsulated with at
least one cationic coating, or with both a cationic coating and a film
forming coating, or with at least one cationic coating, one or more
additional anionic coatings, and a final film former finish.
Cationically-charged fibers encapsulated with the film former are
water-resistant.

[0037] Compositions of the present invention containing the dry, treated
particulates, as described hereinabove, and a suitable vehicle, may also
be provided in a receptacle described above for the dry, treated
particles per se. Optional ingredients which may be formulated into the
compositions may include, but are not limited to, gellants, film formers,
pigments, moisturizers, emollients, humectants, preservatives,
stabilizers, sequestering agents, and the like.

[0038] Treated particulate-containing compositions of the invention may
take the form of a mascara which incorporates the basic formulation
elements of a conventional mascara. Any type of mascara formulation would
be suitable, including aqueous, single oil phase, water-in-oil or
oil-in-water emulsions, and emulsions with three or more phases, with
particulates dispersed in the oil phase of the emulsions.

[0039] Dry, treated particulates prepared according to the present
invention may be present in cosmetic formulations in amounts in the range
of from about 0.1 to about 4 percent by total weight of the formulation.
Preferably, the dry, treated particulates are present in amounts in the
range of from about 0.4 to about 4 percent, such as from about 2 to about
4 percent, by total weight of the formulation. Greater than about 4
percent particulates by total weight of the formulation may be expected
to result in processing issues, including clogging of equipment, and also
non-uniform dispersion in the cosmetic formulation due to agglomeration
of the charged particulates.

[0040] In the case where the compositions are in the form of aqueous
solutions, dispersions or emulsions, in addition to water the aqueous
phase may contain one or more aqueous phase structuring agents, that is,
an agent that increases the viscosity or, or thickens, the aqueous phase
of the composition. This is particularly desirable when the composition
is in the form of a serum or gel. The aqueous phase structuring agent
should be compatible with the optically-activated systems, and also
compatible with the other ingredients in the formulation. Suitable ranges
of aqueous phase structuring agent, if present, are from about 0.01 to
30%, preferably from about 0.1 to 20%, more preferably from about 0.5 to
15% by weight of the total composition. Examples of such agents include
various acrylate based thickening agents, natural or synthetic gums,
polysaccharides, and the like, including but not limited to those set
forth below. As the optically-activated systems are in water soluble
form, an aqueous phase thickening agent also contributes to stabilizing
this ingredient in the composition.

[0042] Also suitable are different types of synthetic polymeric
thickeners. One type includes acrylic polymeric thickeners comprised of
monomers A and B wherein A is selected from the group consisting of
acrylic acid, methacrylic acid, and mixtures thereof; and B is selected
from the group consisting of a C.sub.1-22 alkyl acrylate, a C.sub.1-22
alky methacrylate, and mixtures thereof are suitable. In one embodiment
the A monomer comprises one or more of acrylic acid or methacrylic acid,
and the B monomer is selected from the group consisting of a C.sub.1-10,
most preferably C.sub.1-4 alkyl acrylate, a C.sub.1-10, most preferably
C.sub.1-4 alkyl methacrylate, and mixtures thereof. Most preferably the B
monomer is one or more of methyl or ethyl acrylate or methacrylate. The
acrylic copolymer may be supplied in an aqueous solution having a solids
content ranging from about 10-60%, preferably 20-50%, more preferably
25-45% by weight of the polymer, with the remainder water. The
composition of the acrylic copolymer may contain from about 0.1-99 parts
of the A monomer, and about 0.1-99 parts of the B monomer. Acrylic
polymer solutions include those sold by Seppic, Inc., under the tradename
Capigel.

[0043] Also suitable are acrylic polymeric thickeners that are copolymer
of A, B, and C monomers wherein A and B are as defined above, and C has
the general formula:

##STR00001##

wherein Z is --(CH.sub.2).sub.m; wherein m is 1-10, n is 2-3, o is 2-200,
and R is a C.sub.10-30 straight or branched chain alkyl. Examples of the
secondary thickening agent above, are copolymers where A and B are
defined as above, and C is CO, and wherein n, o, and R are as above
defined. Examples of such secondary thickening agents include
acrylates/steareth-20 methacrylate copolymer, which is sold by Rohm &
Haas under the tradename Acrysol ICS-1.

[0044] Also suitable are acrylate based anionic amphiphilic polymers
containing at least one hydrophilic unit and at least one allyl ether
unit containing a fatty chain. Preferred are those where the hydrophilic
unit contains an ethylenically unsaturated anionic monomer, more
specifically a vinyl carboxylic acid such as acrylic acid, methacrylic
acid or mixtures thereof, and where the allyl ether unit containing a
fatty chain corresponds to the monomer of formula:

CH.sub.2.dbd.CR'CH.sub.2OB.sub.nR

in which R' denotes H or CH.sub.3, B denotes the ethylenoxy radical, n is
zero or an integer ranging from 1 to 100, R denotes a hydrocarbon radical
selected from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals
which contain from 8 to 30 carbon atoms, preferably from 10 to 24, and
even more particularly from 12 to 18 carbon atoms. More preferred in this
case is where R' denotes H, n is equal to 10 and R denotes a stearyl
(C18) radical. Anionic amphiphilic polymers of this type are described
and prepared in U.S. Pat. Nos. 4,677,152 and 4,702,844, both of which are
hereby incorporated by reference in their entirety. Among these anionic
amphiphilic polymers, polymers formed of 20 to 60% by weight acrylic acid
and/or methacrylic acid, of 5 to 60% by weight lower alkyl methacrylates,
of 2 to 50% by weight allyl ether containing a fatty chain as mentioned
above, and of 0 to 1% by weight of a crosslinking agent which is a
well-known copolymerizable polyethylenic unsaturated monomer, for
instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene,
(poly)ethylene glycol dimethacrylate and methylenebisacrylamide. One
commercial example of such polymers are crosslinked terpolymers of
methacrylic acid, of ethyl acrylate, of polyethylene glycol (having 10 EO
units) ether of stearyl alcohol or steareth-10, in particular those sold
by the company Allied Colloids under the names SALCARE SC80 and SALCARE
SC90, which are aqueous emulsions containing 30% of a crosslinked
terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10
allyl ether (40/50/10).

[0045] Also suitable are acrylate copolymers such as Polyacrylate-3 which
is a copolymer of methacrylic acid, methylmethacrylate, methylstyrene
isopropylisocyanate, and PEG-40 behenate monomers; Polyacrylate-10 which
is a copolymer of sodium acryloyldimethyltaurate, sodium acrylate,
acrylamide and vinyl pyrrolidone monomers; or Polyacrylate-11, which is a
copolymer of sodium acryloyldimethylacryloyldimethyl taurate, sodium
acrylate, hydroxyethyl acrylate, lauryl acrylate, butyl acrylate, and
acrylamide monomers.

[0046] Also suitable are crosslinked acrylate based polymers where one or
more of the acrylic groups may have substituted long chain alkyl (such as
6-40, 10-30, and the like) groups, for example acrylates/C.sub.10-30
alkyl acrylate crosspolymer which is a copolymer of C.sub.10-30 alkyl
acrylate and one or more monomers of acrylic acid, methacrylic acid, or
one of their simple esters crosslinked with the allyl ether of sucrose or
the allyl ether of pentaerythritol. Such polymers are commonly sold under
the Carbopol or Pemulen tradenames and have the CTFA name carbomer.

[0047] One particularly suitable type of aqueous phase thickening agent
are acrylate based polymeric thickeners sold by Clariant under the
Aristoflex trademark such as Aristoflex AVC, which is ammonium
acryloyldimethyltaurate/VP copolymer; Aristoflex AVL which is the same
polymer has found in AVC dispersed in mixture containing caprylic/capric
triglyceride, trilaureth-4, and polyglyceryl-2 sesquiisostearate; or
Aristoflex HMB which is ammonium acryloyldimethyltaurate/beheneth-25
methacrylate crosspolymer, and the like.

[0048] Also suitable as the aqueous phase thickening agents are various
polyethylene glycols (PEG) derivatives where the degree of polymerization
ranges from 1,000 to 200,000. Such ingredients are indicated by the
designation "PEG" followed by the degree of polymerization in thousands,
such as PEG-45M, which means PEG having 45,000 repeating ethylene oxide
units. Examples of suitable PEG derivatives include PEG 2M, 5M, 7M, 9M,
14M, 20M, 23M, 25M, 45M, 65M, 90M, 115M, 160M, 180M, and the like.

[0049] Also suitable are polyglycerins which are repeating glycerin
moieties where the number of repeating moieties ranges from 15 to 200,
preferably from about 20-100. Examples of suitable polyglycerins include
those having the CFTA names polyglycerin-20, polyglycerin-40, and the
like.

[0050] In the event the compositions of the invention are in emulsion
form, the composition will comprise an oil phase. Oily ingredients are
desirable for the skin moisturizing and protective properties. Oils, if
present, will form a barrier on the skin so that the optically-activated
complex present in the composition remains on the skin. Suitable oils
include silicones, esters, vegetable oils, synthetic oils, including but
not limited to those set forth herein. The oils may be volatile or
nonvolatile, and are preferably in the form of a pourable liquid at room
temperature. The term "volatile" means that the oil has a measurable
vapor pressure, or a vapor pressure of at least about 2 mm. of mercury at
20.degree. C. The term "nonvolatile" means that the oil has a vapor
pressure of less than about 2 mm. of mercury at 20.degree. C.

[0051] Suitable volatile oils generally have a viscosity ranging from
about 0.5 to 5 centistokes 25.degree. C. and include linear silicones,
cyclic silicones, paraffinic hydrocarbons, or mixtures thereof. Volatile
oils may be used to promote more rapid drying of the skin care
composition after it is applied to skin. Volatile oils are more desirable
when the skin care products containing the optically-activated complex
are being formulated for consumers that have combination or oily skin.
The term "combination" with respect to skin type means skin that is oily
in some places on the face (such as the T-zone) and normal in others.

[0052] Cyclic silicones are one type of volatile silicone that may be used
in the composition. Such silicones have the general formula:

##STR00002##

where n=3-6, preferably 4, 5, or 6.

[0053] Also suitable are linear volatile silicones, for example, those
having the general formula:

[0054] Cyclic and linear volatile silicones are available from various
commercial sources including Dow Corning Corporation and General
Electric. The Dow Corning linear volatile silicones are sold under the
tradenames Dow Corning 244, 245, 344, and 200 fluids. These fluids
include hexamethyldisiloxane (viscosity 0.65 centistokes (abbreviated
cst)), octamethyltrisiloxane (1.0 cst), decamethyltetrasiloxane (1.5
cst), dodecamethylpentasiloxane (2 cst) and mixtures thereof, with all
viscosity measurements being at 25.degree. C.

[0055] Suitable branched volatile silicones include alkyl trimethicones
such as methyl trimethicone, a branched volatile silicone having the
general formula:

##STR00003##

Methyl trimethicone may be purchased from Shin-Etsu Silicones under the
tradename TMF-1.5, having a viscosity of 1.5 centistokes at 25.degree. C.

[0056] Also suitable as the volatile oils are various straight or branched
chain paraffinic hydrocarbons having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,
15, 16, 17, 18, 19, or 20 carbon atoms, more preferably 8 to 16 carbon
atoms. Suitable hydrocarbons include pentane, hexane, heptane, decane,
dodecane, tetradecane, tridecane, and C.sub.8-20 isoparaffins as
disclosed in U.S. Pat. Nos. 3,439,088 and 3,818,105, both of which are
hereby incorporated by reference. Preferred volatile paraffinic
hydrocarbons have a molecular weight of 70-225, preferably 160 to 190 and
a boiling point range of 30 to 320, preferably 60 to 260.degree. C., and
a viscosity of less than about 10 cst. at 25.degree. C. Such paraffinic
hydrocarbons are available from EXXON under the ISOPARS trademark, and
from the Permethyl Corporation. Suitable C.sub.12 isoparaffins are
manufactured by Permethyl Corporation under the tradename Permethyl 99A.
Various C.sub.16 isoparaffins commercially available, such as
isohexadecane (having the tradename Permethyl R), are also suitable.

[0057] A variety of nonvolatile oils are also suitable for use in the
compositions of the invention. The nonvolatile oils generally have a
viscosity of greater than about 5 to 10 centistokes at 25.degree. C., and
may range in viscosity up to about 1,000,000 centipoise at 25.degree. C.
Examples of nonvolatile oils include, but are not limited to:

[0058] Suitable esters are mono-, di-, and triesters. The composition may
comprise one or more esters selected from the group, or mixtures thereof.

[0059] Monoesters are defined as esters formed by the reaction of a
monocarboxylic acid having the formula R--COOH, wherein R is a straight
or branched chain saturated or unsaturated alkyl having 2 to 45 carbon
atoms, or phenyl; and an alcohol having the formula R--OH wherein R is a
straight or branched chain saturated or unsaturated alkyl having 2-30
carbon atoms, or phenyl. Both the alcohol and the acid may be substituted
with one or more hydroxyl groups. Either one or both of the acid or
alcohol may be a "fatty" acid or alcohol, and may have from about 6 to 30
carbon atoms, more preferably 12, 14, 16, 18, or 22 carbon atoms in
straight or branched chain, saturated or unsaturated form. Examples of
monoester oils that may be used in the compositions of the invention
include hexyl laurate, butyl isostearate, hexadecyl isostearate, cetyl
palmitate, isostearyl neopentanoate, stearyl heptanoate, isostearyl
isononanoate, stearyl lactate, stearyl octanoate, stearyl stearate,
isononyl isononanoate, and so on.

[0060] Suitable diesters are the reaction product of a dicarboxylic acid
and an aliphatic or aromatic alcohol or an aliphatic or aromatic alcohol
having at least two substituted hydroxyl groups and a monocarboxylic
acid. The dicarboxylic acid may contain from 2 to 30 carbon atoms, and
may be in the straight or branched chain, saturated or unsaturated form.
The dicarboxylic acid may be substituted with one or more hydroxyl
groups. The aliphatic or aromatic alcohol may also contain 2 to 30 carbon
atoms, and may be in the straight or branched chain, saturated, or
unsaturated form. Preferably, one or more of the acid or alcohol is a
fatty acid or alcohol, i.e. contains 12-22 carbon atoms. The dicarboxylic
acid may also be an alpha hydroxy acid. The ester may be in the dimer or
trimer form. Examples of diester oils that may be used in the
compositions of the invention include diisotearyl malate, neopentyl
glycol dioctanoate, dibutyl sebacate, dicetearyl dimer dilinoleate,
dicetyl adipate, diisocetyl adipate, diisononyl adipate, diisostearyl
dimer dilinoleate, diisostearyl fumarate, diisostearyl malate, dioctyl
malate, and so on.

[0061] Suitable triesters comprise the reaction product of a tricarboxylic
acid and an aliphatic or aromatic alcohol or alternatively the reaction
product of an aliphatic or aromatic alcohol having three or more
substituted hydroxyl groups with a monocarboxylic acid. As with the mono-
and diesters mentioned above, the acid and alcohol contain 2 to 30 carbon
atoms, and may be saturated or unsaturated, straight or branched chain,
and may be substituted with one or more hydroxyl groups. Preferably, one
or more of the acid or alcohol is a fatty acid or alcohol containing 12
to 22 carbon atoms. Examples of triesters include esters of arachidonic,
citric, or behenic acids, such as triarachidin, tributyl citrate,
triisostearyl citrate, tri C.sub.12-13 alkyl citrate, tricaprylin,
tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate, tridecyl
behenate; or tridecyl cocoate, tridecyl isononanoate, and so on.

[0062] Esters suitable for use in the composition are further described in
the C.T.F.A. Cosmetic Ingredient Dictionary and Handbook, Eleventh
Edition, 2006, under the classification of "Esters", the text of which is
hereby incorporated by reference in its entirety.

[0063] It may be desirable to incorporate one or more nonvolatile
hydrocarbon oils into the composition. Suitable nonvolatile hydrocarbon
oils include paraffinic hydrocarbons and olefins, preferably those having
greater than about 20 carbon atoms. Examples of such hydrocarbon oils
include C.sub.24-28 olefins, C.sub.30-45 olefins, C.sub.20-40
isoparaffins, hydrogenated polyisobutene, polyisobutene, polydecene,
hydrogenated polydecene, mineral oil, pentahydrosqualene, squalene,
squalane, and mixtures thereof. In one preferred embodiment such
hydrocarbons have a molecular weight ranging from about 300 to 1000
Daltons.

[0066] Nonvolatile silicone oils, both water soluble and water insoluble,
are also suitable for use in the composition. Such silicones preferably
have a viscosity ranging from about greater than 5 to 800,000 cst,
preferably 20 to 200,000 cst at 25.degree. C. Suitable water insoluble
silicones include amine functional silicones such as amodimethicone.

[0067] For example, such nonvolatile silicones may have the following
general formula:

##STR00004##

wherein R and R' are each independently C.sub.1-30 straight or branched
chain, saturated or unsaturated alkyl, phenyl or aryl, trialkylsiloxy,
and x and y are each independently 1-1,000,000; with the proviso that
there is at least one of either x or y, and A is alkyl siloxy endcap
unit. Preferred is where A is a methyl siloxy endcap unit; in particular
trimethylsiloxy, and R and R' are each independently a C.sub.1-30
straight or branched chain alkyl, phenyl, or trimethylsiloxy, more
preferably a C.sub.1-22 alkyl, phenyl, or trimethylsiloxy, most
preferably methyl, phenyl, or trimethylsiloxy, and resulting silicone is
dimethicone, phenyl dimethicone, diphenyl dimethicone, phenyl
trimethicone, or trimethylsiloxyphenyl dimethicone. Other examples
include alkyl dimethicones such as cetyl dimethicone, and the like
wherein at least one R is a fatty alkyl (C.sub.12, C.sub.14, C.sub.16,
C.sub.18, C.sub.20, or C.sub.22), and the other R is methyl, and A is a
trimethylsiloxy endcap unit, provided such alkyl dimethicone is a
pourable liquid at room temperature. Phenyl trimethicone can be purchased
from Dow Corning Corporation under the tradename 556 Fluid.
Trimethylsiloxyphenyl dimethicone can be purchased from Wacker-Chemie
under the tradename PDM-1000. Cetyl dimethicone, also referred to as a
liquid silicone wax, may be purchased from Dow Corning as Fluid 2502, or
from DeGussa Care & Surface Specialties under the trade names Abil Wax
9801, or 9814.

[0068] Various types of fluorinated oils may also be suitable for use in
the compositions including but not limited to fluorinated silicones,
fluorinated esters, or perfluropolyethers. Particularly suitable are
fluorosilicones such as trimethylsilyl endcapped fluorosilicone oil,
polytrifluoropropylmethylsiloxanes, and similar silicones such as those
disclosed in U.S. Pat. No. 5,118,496 which is hereby incorporated by
reference. Perfluoropolyethers include those disclosed in U.S. Pat. Nos.
5,183,589, 4,803,067, 5,183,588 all of which are hereby incorporated by
reference, which are commercially available from Montefluos under the
trademark Fomblin.

[0069] In the case where the composition is anhydrous or in the form of an
emulsion, it may be desirable to include one or more oil phase
structuring agents in the cosmetic composition. The term "oil phase
structuring agent" means an ingredient or combination of ingredients,
soluble or dispersible in the oil phase, which will increase the
viscosity, or structure, the oil phase. The oil phase structuring agent
is compatible with the optically-activated complex, particularly if the
optically-activated complex may be solubilized in the nonpolar oils
forming the oil phase of the composition. The term "compatible" means
that the oil phase structuring agent and optically-activated complex are
capable of being formulated into a cosmetic product that is generally
stable. The structuring agent may be present in an amount sufficient to
provide a liquid composition with increased viscosity, a semi-solid, or
in some cases a solid composition that may be self-supporting. The
structuring agent itself may be present in the liquid, semi-solid, or
solid form. Suggested ranges of structuring agent are from about 0.01 to
70%, preferably from about 0.05 to 50%, more preferably from about
0.1-35% by weight of the total composition. Suitable oil phase
structuring agents include those that are silicone based or organic
based. They may be polymers or non-polymers, synthetic, natural, or a
combination of both.

[0070] A variety of oil phase structuring agents may be silicone based,
such as silicone elastomers, silicone gums, silicone waxes, linear
silicones having a degree of polymerization that provides the silicone
with a degree of viscosity such that when incorporated into the cosmetic
composition it is capable of increasing the viscosity of the oil phase.
Examples of silicone structuring agents include, but are not limited to
the following.

[0071] Silicone elastomers suitable for use in the compositions of the
invention include those that are formed by addition reaction-curing, by
reacting an SiH-containing diorganosiloxane and an organopolysiloxane
having terminal olefinic unsaturation, or an alpha-omega diene
hydrocarbon, in the presence of a platinum metal catalyst. Such
elastomers may also be formed by other reaction methods such as
condensation-curing organopolysiloxane compositions in the presence of an
organotin compound via a dehydrogenation reaction between
hydroxyl-terminated diorganopolysiloxane and SiH-containing
diorganopolysiloxane or alpha omega diene; or by condensation-curing
organopolysiloxane compositions in the presence of an organotin compound
or a titanate ester using a condensation reaction between an
hydroxyl-terminated diorganopolysiloxane and a hydrolysable
organosiloxane; peroxide-curing organopolysiloxane compositions which
thermally cure in the presence of an organoperoxide catalyst.

[0072] One type of elastomer that may be suitable is prepared by addition
reaction-curing an organopolysiloxane having at least 2 lower alkenyl
groups in each molecule or an alpha-omega diene; and an
organopolysiloxane having at least 2 silicon-bonded hydrogen atoms in
each molecule; and a platinum-type catalyst. While the lower alkenyl
groups such as vinyl, can be present at any position in the molecule,
terminal olefinic unsaturation on one or both molecular terminals is
preferred. The molecular structure of this component may be straight
chain, branched straight chain, cyclic, or network. These
organopolysiloxanes are exemplified by methylvinylsiloxanes,
methylvinylsiloxane-dimethylsiloxane copolymers,
dimethylvinylsiloxy-terminated dimethylpolysiloxanes,
dimethylvinylsiloxy-terminated dimethyl siloxane-methylphenylsiloxane
copolymers, dimethylvinylsiloxy-terminated
dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymers,
trimethylsiloxy-terminated dimethyl siloxane-methylvinylsiloxane
copolymers, trimethylsiloxy-terminated
dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers,
dimethylvinylsiloxy-terminated methyl(3,3,3-trifluoropropyl)
polysiloxanes, and dimethylvinylsiloxy-terminated
dimethylsiloxane-methyl(3,3,-trifluoropropyl)siloxane copolymers,
decadiene, octadiene, heptadiene, hexadiene, pentadiene, or tetradiene,
or tridiene.

[0073] Curing proceeds by the addition reaction of the silicon-bonded
hydrogen atoms in the dimethyl methylhydrogen siloxane, with the siloxane
or alpha-omega diene under catalysis using the catalyst mentioned herein.
To form a highly crosslinked structure, the methyl hydrogen siloxane must
contain at least 2 silicon-bonded hydrogen atoms in each molecule in
order to optimize function as a crosslinker.

[0074] The catalyst used in the addition reaction of silicon-bonded
hydrogen atoms and alkenyl groups, and is concretely exemplified by
chloroplatinic acid, possibly dissolved in an alcohol or ketone and this
solution optionally aged, chloroplatinic acid-olefin complexes,
chloroplatinic acid-alkenylsiloxane complexes, chloroplatinic
acid-diketone complexes, platinum black, and carrier-supported platinum.

[0075] Examples of suitable silicone elastomers for use in the
compositions of the invention may be in the powder form, or dispersed or
solubilized in solvents such as volatile or non-volatile silicones, or
silicone compatible vehicles such as paraffinic hydrocarbons or esters.
Examples of silicone elastomer powders include vinyl
dimethicone/methicone silesquioxane crosspolymers like Shin-Etsu's
KSP-100, KSP-101, KSP-102, KSP-103, KSP-104, KSP-105, hybrid silicone
powders that contain a fluoroalkyl group like Shin-Etsu's KSP-200 which
is a fluoro-silicone elastomer, and hybrid silicone powders that contain
a phenyl group such as Shin-Etsu's KSP-300, which is a phenyl substituted
silicone elastomer; and Dow Coming's DC 9506. Examples of silicone
elastomer powders dispersed in a silicone compatible vehicle include
dimethicone/vinyl dimethicone crosspolymers supplied by a variety of
suppliers including Dow Corning Corporation under the tradenames 9040 or
9041, GE Silicones under the tradename SFE 839, or Shin-Etsu Silicones
under the tradenames KSG-15, 16, 18. KSG-15 has the CTFA name
cyclopentasiloxane/dimethicone/vinyl dimethicone crosspolymer. KSG-18 has
the INCI name phenyl trimethicone/dimethicone/phenyl vinyl dimethicone
crossoplymer. Silicone elastomers may also be purchased from Grant
Industries under the Gransil trademark. Also suitable are silicone
elastomers having long chain alkyl substitutions such as lauryl
dimethicone/vinyl dimethicone crosspolymers supplied by Shin Etsu under
the tradenames KSG-31, KSG-32, KSG-41, KSG-42, KSG-43, and KSG-44.
Cross-linked organopolysiloxane elastomers useful in the present
invention and processes for making them are further described in U.S.
Pat. No. 4,970,252 to Sakuta et al., issued Nov. 13, 1990; U.S. Pat. No.
5,760,116 to Kilgour et al., issued Jun. 2, 1998; U.S. Pat. No. 5,654,362
to Schulz, Jr. et al. issued Aug. 5, 1997; and Japanese Patent
Application JP 61-18708, assigned to Pola Kasei Kogyo KK, each of which
are herein incorporated by reference in its entirety. It is particularly
desirable to incorporate silicone elastomers into the compositions of the
invention because they provide excellent "feel" to the composition, are
very stable in cosmetic formulations, and relatively inexpensive.

[0076] Also suitable for use as an oil phase structuring agent are one or
more silicone gums. The term "gum" means a silicone polymer having a
degree of polymerization sufficient to provide a silicone having a
gum-like texture. In certain cases the silicone polymer forming the gum
may be crosslinked. The silicone gum typically has a viscosity ranging
from about 500,000 to 100 million cst at 25.degree. C., preferably from
about 600,000 to 20 million, more preferably from about 600,000 to 12
million cst. All ranges mentioned herein include all subranges, e.g.
550,000; 925,000; 3.5 million.

[0077] The silicone gums that are used in the compositions include, but
are not limited to, those of the general formula:

##STR00005##

wherein R.sub.1 to R.sub.9 are each independently an alkyl having 1 to 30
carbon atoms, aryl, or aralkyl; and X is OH or a C.sub.1-30 alkyl, or
vinyl; and wherein x, y, or z may be zero with the proviso that no more
than two of x, y, or z are zero at any one time, and further that x, y,
and z are such that the silicone gum has a viscosity of at least about
500,000 cst, ranging up to about 100 million centistokes at 25.degree. C.
Preferred is where R is methyl or OH.

[0078] Such silicone gums may be purchased in pure form from a variety of
silicone manufacturers including Wacker-Chemie or Dow Corning, and the
like. Such silicone gums include those sold by Wacker-Belsil under the
trade names CM3092, Wacker-Belsil 1000, or Wacker-Belsil DM 3096. A
silicone gum where X is OH, also referred to as dimethiconol, is
available from Dow Corning Corporation under the trade name 1401. The
silicone gum may also be purchased in the form of a solution or
dispersion in a silicone compatible vehicle such as volatile or
nonvolatile silicone. An example of such a mixture may be purchased from
Barnet Silicones under the HL-88 tradename, having the INCI name
dimethicone.

[0079] Another type of oily phase structuring agent includes silicone
waxes that are typically referred to as alkyl silicone waxes which are
semi-solids or solids at room temperature. The term "alkyl silicone wax"
means a polydimethylsiloxane having a substituted long chain alkyl (such
as C16 to 30) that confers a semi-solid or solid property to the
siloxane. Examples of such silicone waxes include stearyl dimethicone,
which may be purchased from DeGussa Care & Surface Specialties under the
tradename Abil Wax 9800 or from Dow Corning under the tradename 2503.
Another example is bis-stearyl dimethicone, which may be purchased from
Gransil Industries under the tradename Gransil A-18, or behenyl
dimethicone, behenoxy dimethicone.

[0080] Also suitable as oil phase structuring agents are various types of
polymeric compounds such as polyamides or silicone polyamides.

[0081] The term silicone polyamide means a polymer comprised of silicone
monomers and monomers containing amide groups as further described
herein. The silicone polyamide preferably comprises moieties of the
general formula:

##STR00006##

wherein X is a linear or branched alkylene having from about 1-30 carbon
atoms; R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently
C.sub.1-30 straight or branched chain alkyl which may be substituted with
one or more hydroxyl or halogen groups; phenyl which may be substituted
with one or more C.sub.1-30 alkyl groups, halogen, hydroxyl, or alkoxy
groups; or a siloxane chain having the general formula:

##STR00007##

and Y is:

[0082] (a) a linear or branched alkylene having from about 1-40 carbon
atoms which may be substituted with: [0083] (i) one or more amide groups
having the general formula R.sub.1CONR.sub.1, or [0084] (ii) C.sub.5-6
cyclic ring, or [0085] (iii) phenylene which may be substituted with one
or more C.sub.1-10 alkyl groups, or [0086] (iv) hydroxy, or [0087] (v)
C.sub.3-8 cycloalkane, or [0088] (vi) C.sub.1-20 alkyl which may be
substituted with one or more hydroxy groups, or [0089] (vii) C.sub.1-10
alkyl amines; or [0090] (b) TR.sub.5R.sub.6R.sub.7 wherein R.sub.5,
R.sub.6, and R.sub.7, are each independently a C.sub.1-10 linear or
branched alkylenes, and T is CR.sub.8 wherein R.sub.8 is hydrogen, a
trivalent atom N, P, or Al, or a C.sub.1-30 straight or branched chain
alkyl which may be substituted with one or more hydroxyl or halogen
groups; phenyl which may be substituted with one or more C.sub.1-30 alkyl
groups, halogen, hydroxyl, or alkoxy groups; or a siloxane chain having
the general formula:

##STR00008##

[0091] Preferred is where R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are
C.sub.1-10, preferably methyl; and X and Y is a linear or branched
alkylene. Preferred are silicone polyamides having the general formula:

##STR00009##

wherein a and b are each independently sufficient to provide a silicone
polyamide polymer having a melting point ranging from about 60 to
120.degree. C., and a molecular weight ranging from about 40,000 to
500,000 Daltons. One type of silicone polyamide that may be used in the
compositions of the invention may be purchased from Dow Corning
Corporation under the tradename Dow Corning 2-8178 gellant which has the
CTFA name nylon-611/dimethicone copolymer which is sold in a composition
containing PPG-3 myristyl ether. Also suitable are polyamides such as
those purchased from Arizona Chemical under the tradenames Uniclear and
Sylvaclear. Such polyamides may be ester terminated or amide terminated.
Examples of ester terminated polyamides include, but are not limited to
those having the general formula:

##STR00010##

wherein n denotes a number of amide units such that the number of ester
groups ranges from about 10% to 50% of the total number of ester and
amide groups; each R.sup.1 is independently an alkyl or alkenyl group
containing at least 4 carbon atoms; each R.sup.2 is independently a
C.sub.4-42 hydrocarbon group, with the proviso that at least 50% of the
R.sup.2 groups are a C30-42 hydrocarbon; each R.sup.3 is independently an
organic group containing at least 2 carbon atoms, hydrogen atoms and
optionally one or more oxygen or nitrogen atoms; and each R.sup.4 is
independently a hydrogen atom, a C.sub.1-10 alkyl group or a direct bond
to R.sup.3 or to another R.sup.4, such that the nitrogen atom to which
R.sup.3 and R.sup.4 are both attached forms part of a heterocyclic
structure defined by R.sup.4--N--R.sup.3, with at least 50% of the groups
R.sub.4 representing a hydrogen atom.

[0092] General examples of ester and amide terminated polyamides that may
be used as oil phase gelling agents include those sold by Arizona
Chemical under the tradenames Sylvaclear A200V or A2614V, both having the
CTFA name ethylenediamine/hydrogenated dimer dilinoleate
copolymer/bis-di-C.sub.14-18 alkyl amide; Sylvaclear AF1900V; Sylvaclear
C75V having the CTFA name bis-stearyl ethylenediamine/neopentyl
glycol/stearyl hydrogenated dimer dilinoleate copolymer; Sylvaclear
PA1200V having the CTFA name Polyamide-3; Sylvaclear PE400V; Sylvaclear
WF1500V; or Uniclear, such as Uniclear 100VG having the INCI name
ethylenediamine/stearyl dimer dilinoleate copolymer; or
ethylenediamine/stearyl dimer ditallate copolymer. Other examples of
suitable polyamides include those sold by Henkel under the Versamid
trademark (such as Versamid 930, 744, 1655), or by Olin Mathieson
Chemical Corp. under the brand name Onamid S or Onamid C.

[0093] Also suitable as the oil phase structuring agent may be one or more
natural or synthetic waxes such as animal, vegetable, or mineral waxes.
Preferably such waxes will have a higher melting point such as from about
50 to 150.degree. C., more preferably from about 65 to 100.degree. C.
Examples of such waxes include waxes made by Fischer-Tropsch synthesis,
such as polyethylene or synthetic wax; or various vegetable waxes such as
bayberry, candelilla, ozokerite, acacia, beeswax, ceresin, cetyl esters,
flower wax, citrus wax, carnauba wax, jojoba wax, japan wax,
polyethylene, microcrystalline, rice bran, lanolin wax, mink, montan,
bayberry, ouricury, ozokerite, palm kernel wax, paraffin, avocado wax,
apple wax, shellac wax, clary wax, spent grain wax, grape wax, and
polyalkylene glycol derivatives thereof such as PEG6-20 beeswax, or
PEG-12 carnauba wax; or fatty acids or fatty alcohols, including esters
thereof, such as hydroxystearic acids (for example 12-hydroxy stearic
acid), tristearin, tribehenin, and so on.

[0094] One type of structuring agent that may be used in the composition
comprises natural or synthetic montmorillonite minerals such as
hectorite, bentonite, and quaternized derivatives thereof, which are
obtained by reacting the minerals with a quaternary ammonium compound,
such as stearalkonium bentonite, hectorites, quaternized hectorites such
as Quaternium-18 hectorite, attapulgite, carbonates such as propylene
carbonate, bentones, and the like.

[0095] Another type of structuring agent that may be used in the
compositions are silicas, silicates, silica silylate, and alkali metal or
alkaline earth metal derivatives thereof. These silicas and silicates are
generally found in the particulate form and include silica, silica
silylate, magnesium aluminum silicate, and the like.

[0096] The composition may contain one or more surfactants, especially if
in the emulsion form. However, such surfactants may be used if the
compositions are anhydrous also, and will assist in dispersing
ingredients that have polarity, for example pigments. Such surfactants
may be silicone or organic based. The surfactants will aid in the
formation of stable emulsions of either the water-in-oil or oil-in-water
form. If present, the surfactant may range from about 0.001 to 30%,
preferably from about 0.005 to 25%, more preferably from about 0.1 to 20%
by weight of the total composition.

[0097] Suitable silicone surfactants include polyorganosiloxane polymers
that have amphiphilic properties, for example contain hydrophilic
radicals and lipophilic radicals. These silicone surfactants may be
liquids or solids at room temperature.

[0098] One type of silicone surfactant that may be used is generally
referred to as dimethicone copolyol or alkyl dimethicone copolyol. This
surfactant is either a water-in-oil or oil-in-water surfactant having an
Hydrophile/Lipophile Balance (HLB) ranging from about 2 to 18. Preferably
the silicone surfactant is a nonionic surfactant having an HLB ranging
from about 2 to 12, preferably about 2 to 10, most preferably about 4 to
6. The term "hydrophilic radical" means a radical that, when substituted
onto the organosiloxane polymer backbone, confers hydrophilic properties
to the substituted portion of the polymer. Examples of radicals that will
confer hydrophilicity are hydroxy-polyethyleneoxy, hydroxyl,
carboxylates, and mixtures thereof. The term "lipophilic radical" means
an organic radical that, when substituted onto the organosiloxane polymer
backbone, confers lipophilic properties to the substituted portion of the
polymer. Examples of organic radicals that will confer lipophilicity are
C.sub.1-40 straight or branched chain alkyl, fluoro, aryl, aryloxy,
C.sub.1-40 hydrocarbyl acyl, hydroxy-polypropyleneoxy, or mixtures
thereof.

[0099] One type of suitable silicone surfactant has the general formula:

##STR00011##

wherein p is 0-40 (the range including all numbers between and subranges
such as 2, 3, 4, 13, 14, 15, 16, 17, 18, etc.), and PE is
(--C.sub.2H.sub.4O).sub.a--(--C.sub.3H.sub.6O).sub.b--H wherein a is 0 to
25, b is 0-25 with the proviso that both a and b cannot be 0
simultaneously, x and y are each independently ranging from 0 to 1
million with the proviso that they both cannot be 0 simultaneously. In
one preferred embodiment, x, y, z, a, and b are such that the molecular
weight of the polymer ranges from about 5,000 to about 500,000, more
preferably from about 10,000 to 100,000, and is most preferably
approximately about 50,000 and the polymer is generically referred to as
dimethicone copolyol.

[0100] One type of silicone surfactant is wherein p is such that the long
chain alkyl is cetyl or lauryl, and the surfactant is called,
generically, cetyl dimethicone copolyol or lauryl dimethicone copolyol
respectively.

[0101] In some cases the number of repeating ethylene oxide or propylene
oxide units in the polymer are also specified, such as a dimethicone
copolyol that is also referred to as PEG-15/PPG-10 dimethicone, which
refers to a dimethicone having substituents containing 15 ethylene glycol
units and 10 propylene glycol units on the siloxane backbone. It is also
possible for one or more of the methyl groups in the above general
structure to be substituted with a longer chain alkyl (e.g. ethyl,
propyl, butyl, etc.) or an ether such as methyl ether, ethyl ether,
propyl ether, butyl ether, and the like.

[0102] Examples of silicone surfactants are those sold by Dow Corning
under the tradename Dow Corning 3225C Formulation Aid having the CTFA
name cyclotetrasiloxane (and) cyclopentasiloxane (and) PEG/PPG-18
dimethicone; or 5225C Formulation Aid, having the CTFA name
cyclopentasiloxane (and) PEG/PPG-18/18 dimethicone; or Dow Coming 190
Surfactant having the CTFA name PEG/PPG-18/18 dimethicone; or Dow Corning
193 Fluid, Dow Corning 5200 having the CTFA name lauryl PEG/PPG-18/18
methicone; or Abil EM 90 having the CTFA name cetyl PEG/PPG-14/14
dimethicone sold by Goldschmidt; or Abil EM 97 having the CTFA name
bis-cetyl PEG/PPG-14/14 dimethicone sold by Goldschmidt; or Abil WE 09
having the CTFA name cetyl PEG/PPG-10/1 dimethicone in a mixture also
containing polyglyceryl-4 isostearate and hexyl laurate; or KF-6011 sold
by Shin-Etsu Silicones having the CTFA name PEG-11 methyl ether
dimethicone; KF-6012 sold by Shin-Etsu Silicones having the CTFA name
PEG/PPG-20/22 butyl ether dimethicone; or KF-6013 sold by Shin-Etsu
Silicones having the CTFA name PEG-9 dimethicone; or KF-6015 sold by
Shin-Etsu Silicones having the CTFA name PEG-3 dimethicone; or KF-6016
sold by Shin-Etsu Silicones having the CTFA name PEG-9 methyl ether
dimethicone; or KF-6017 sold by Shin-Etsu Silicones having the CTFA name
PEG-10 dimethicone; or KF-6038 sold by Shin-Etsu Silicones having the
CTFA name lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

[0103] Also suitable are various types of crosslinked silicone surfactants
that are often referred to as emulsifying elastomers. They are typically
prepared as set forth above with respect to the section "silicone
elastomers" except that the silicone elastomers will contain at least one
hydrophilic moiety such as polyoxyalkylenated groups. Typically these
polyoxyalkylenated silicone elastomers are crosslinked
organopolysiloxanes that may be obtained by a crosslinking addition
reaction of diorganopolysiloxane comprising at least one hydrogen bonded
to silicon and of a polyoxyalkylene comprising at least two ethylenically
unsaturated groups. In at least one embodiment, the polyoxyalkylenated
crosslinked organo-polysiloxanes are obtained by a crosslinking addition
reaction of a diorganopolysiloxane comprising at least two hydrogens each
bonded to a silicon, and a polyoxyalkylene comprising at least two
ethylenically unsaturated groups, optionally in the presence of a
platinum catalyst, as described, for example, in U.S. Pat. No. 5,236,986
and U.S. Pat. No. 5,412,004, U.S. Pat. No. 5,837,793 and U.S. Pat. No.
5,811,487, the contents of which are incorporated by reference.

[0104] Polyoxyalkylenated silicone elastomers that may be used in at least
one embodiment of the invention include those sold by Shin-Etsu Silicones
under the names KSG-21, KSG-20, KSG-30, KSG-31, KSG-32, KSG-33; KSG-210
which is dimethicone/PEG-10/15 crosspolymer dispersed in dimethicone;
KSG-310 which is PEG-15 lauryl dimethicone crosspolymer; KSG-320 which is
PEG-15 lauryl dimethicone crosspolymer dispersed in isododecane; KSG-330
(the former dispersed in triethylhexanoin), KSG-340 which is a mixture of
PEG-10 lauryl dimethicone crosspolymer and PEG-15 lauryl dimethicone
crosspolymer.

[0105] Also suitable are polyglycerolated silicone elastomers like those
disclosed in PCT/WO 2004/024798, which is hereby incorporated by
reference in its entirety. Such elastomers include Shin-Etsu's KSG
series, such as KSG-710 which is dimethicone/polyglycerin-3 crosspolymer
dispersed in dimethicone; or lauryl dimethicone/polyglycerin-3
crosspolymer dispersed in a variety of solvent such as isododecane,
dimethicone, triethylhexanoin, sold under the Shin-Etsu tradenames
KSG-810, KSG-820, KSG-830, or KSG-840. Also suitable are silicones sold
by Dow Corning under the tradenames 9010 and DC9011. One preferred
crosslinked silicone elastomer emulsifier is dimethicone/PEG-10/15
crosspolymer, which provides excellent aesthetics due to its elastomeric
backbone, but also surfactancy properties.

[0106] The composition may comprise one or more nonionic organic
surfactants. Suitable nonionic surfactants include alkoxylated alcohols,
or ethers, formed by the reaction of an alcohol with an alkylene oxide,
usually ethylene or propylene oxide. Preferably the alcohol is either a
fatty alcohol having 6 to 30 carbon atoms. Examples of such ingredients
include Steareth 2-100, which is formed by the reaction of stearyl
alcohol and ethylene oxide and the number of ethylene oxide units ranges
from 2 to 100; Beheneth 5-30 which is formed by the reaction of behenyl
alcohol and ethylene oxide where the number of repeating ethylene oxide
units is 5 to 30; Ceteareth 2-100, formed by the reaction of a mixture of
cetyl and stearyl alcohol with ethylene oxide, where the number of
repeating ethylene oxide units in the molecule is 2 to 100; Ceteth 1-45
which is formed by the reaction of cetyl alcohol and ethylene oxide, and
the number of repeating ethylene oxide units is 1 to 45, and so on.

[0107] Other alkoxylated alcohols are formed by the reaction of fatty
acids and mono-, di- or polyhydric alcohols with an alkylene oxide. For
example, the reaction products of C.sub.6-30 fatty carboxylic acids and
polyhydric alcohols which are monosaccharides such as glucose, galactose,
methyl glucose, and the like, with an alkoxylated alcohol. Examples
include polymeric alkylene glycols reacted with glyceryl fatty acid
esters such as PEG glyceryl oleates, PEG glyceryl stearate; or PEG
polyhydroxyalkanotes such as PEG dipolyhydroxystearate wherein the number
of repeating ethylene glycol units ranges from 3 to 1000.

[0108] Also suitable as nonionic surfactants are formed by the reaction of
a carboxylic acid with an alkylene oxide or with a polymeric ether. The
resulting products have the general formula:

##STR00012##

where RCO is the carboxylic ester radical, X is hydrogen or lower alkyl,
and n is the number of polymerized alkoxy groups. In the case of the
diesters, the two RCO-groups do not need to be identical. Preferably, R
is a C6-30 straight or branched chain, saturated or unsaturated alkyl,
and n is from 1-100.

[0109] Monomeric, homopolymeric, or block copolymeric ethers are also
suitable as nonionic surfactants. Typically, such ethers are formed by
the polymerization of monomeric alkylene oxides, generally ethylene or
propylene oxide. Such polymeric ethers have the following general
formula:

##STR00013##

wherein R is H or lower alkyl and n is the number of repeating monomer
units, and ranges from 1 to 500.

[0111] Certain types of amphoteric, zwitterionic, or cationic surfactants
may also be used in the compositions. Descriptions of such surfactants
are set forth in U.S. Pat. No. 5,843,193, which is hereby incorporated by
reference in its entirety.

[0112] It may also be desirable to include one or more humectants in the
composition. If present, such humectants may range from about 0.001 to
25%, preferably from about 0.005 to 20%, more preferably from about 0.1
to 15% by weight of the total composition. Examples of suitable
humectants include glycols, sugars, and the like. Suitable glycols are in
monomeric or polymeric form and include polyethylene and polypropylene
glycols such as PEG 4-200, which are polyethylene glycols having from 4
to 200 repeating ethylene oxide units; as well as C.sub.1-6 alkylene
glycols such as propylene glycol, butylene glycol, pentylene glycol, and
the like. Suitable sugars, some of which are also polyhydric alcohols,
are also suitable humectants. Examples of such sugars include glucose,
fructose, honey, hydrogenated honey, inositol, maltose, mannitol,
maltitol, sorbitol, sucrose, xylitol, xylose, and so on. Also suitable is
urea.

[0114] It may also be desirable to include one or more sunscreens in the
compositions of the invention. Such sunscreens include chemical UVA or
UVB sunscreens or physical sunscreens in the particulate form. Inclusion
of sunscreens in the compositions containing the optically-activated
complex will provide additional protection to skin during daylight hours.

[0115] If desired, the composition may comprise one or more UVA
sunscreens. The term "UVA sunscreen" means a chemical compound that
blocks UV radiation in the wavelength range of about 320 to 400 nm.
Preferred UVA sunscreens are dibenzoylmethane compounds having the
general formula:

##STR00014##

wherein R.sub.1 is H, OR and NRR wherein each R is independently H,
C.sub.1-20 straight or branched chain alkyl; R.sub.2 is H or OH; and
R.sub.3 is H, C.sub.1-20 straight or branched chain alkyl.

[0116] Preferred is where R.sub.1 is OR where R is a C.sub.1-20 straight
or branched alkyl, preferably methyl; R.sub.2 is H; and R.sub.3 is a
C.sub.1-20 straight or branched chain alkyl, more preferably, butyl.

[0117] Examples of suitable UVA sunscreen compounds of this general
formula include 4-methyldibenzoylmethane, 2-methyldibenzoylmethane, 4-i
sopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane,
2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane,
4,4'diisopropylbenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane,
4,4'-diisopropylbenzoylmethane,
2-methyl-5-isopropyl-4'-methoxydibenzoymethane,
2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, and so on. Particularly
preferred is 4-tert-butyl-4'-methoxydibenzoylmethane, also referred to as
Avobenzone. Avobenzone is commercial available from Givaudan-Roure under
the trademark Parsol 1789, and Merck & Co. under the tradename Eusolex
9020.

[0118] Other types of UVA sunscreens include dicamphor sulfonic acid
derivatives, such as ecamsule, a sunscreen sold under the trade name
Mexoryl.TM., which is terephthalylidene dicamphor sulfonic acid, having
the formula:

##STR00015##

[0119] The composition may contain from about 0.001-20%, preferably
0.005-5%, more preferably about 0.005-3% by weight of the composition of
UVA sunscreen. In the preferred embodiment of the invention the UVA
sunscreen is Avobenzone, and it is present at not greater than about 3%
by weight of the total composition.

[0120] UVB sunscreens may also be employed in the systems of the present
invention. The term "UVB sunscreen" means a compound that blocks UV
radiation in the wavelength range of from about 290 to 320 nm. A variety
of UVB chemical sunscreens exist including alpha-cyano-beta,beta-diphenyl
acrylic acid esters as set forth in U.S. Pat. No. 3,215,724, which is
hereby incorporated by reference in its entirety. One particular example
of an alpha-cyano-beta,beta-diphenyl acrylic acid ester is Octocrylene,
which is 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. In certain cases the
composition may contain no more than about 110% by weight of the total
composition of octocrylene. Suitable amounts range from about 0.001-10%
by weight. Octocrylene may be purchased from BASF under the tradename
Uvinul N-539.

[0121] Other suitable sunscreens include benzylidene camphor derivatives
as set forth in U.S. Pat. No. 3,781,417, which is hereby incorporated by
reference in its entirety. Such benzylidene camphor derivatives have the
general formula:

##STR00016##

wherein R is p-tolyl or styryl, preferably styryl. Particularly preferred
is 4-methylbenzylidene camphor, which is a lipid soluble UVB sunscreen
compound sold under the tradename Eusolex 6300 by Merck.

[0122] Also suitable are cinnamate derivatives having the general formula:

##STR00017##

wherein R and R.sub.1 are each independently a C.sub.1-20 straight or
branched chain alkyl. Preferred is where R is methyl and R.sub.1 is a
branched chain C.sub.1-10, preferably C.sub.8 alkyl. The preferred
compound is ethylhexyl methoxycinnamate, also referred to as Octoxinate
or octyl methoxycinnamate. The compound may be purchased from Givaudan
Corporation under the tradename Parsol MCX, or BASF under the tradename
Uvinul MC 80. Also suitable are mono-, di-, and triethanolamine
derivatives of such methoxy cinnamates including diethanolamine
methoxycinnamate. Cinoxate, the aromatic ether derivative of the above
compound is also acceptable. If present, the Cinoxate should be found at
no more than about 3% by weight of the total composition.

[0123] Also suitable as UVB screening agents are various benzophenone
derivatives having the general formula:

[0124] Also suitable are certain menthyl salicylate derivatives having the
general formula:

##STR00019##

wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently H,
OH, NH.sub.2, or C.sub.1-20 straight or branched chain alkyl.
Particularly preferred is where R.sub.1, R.sub.2, and R.sub.3 are methyl
and R.sub.4 is hydroxyl or NH.sub.2, the compound having the name
homomenthyl salicylate (also known as Homosalate) or menthyl
anthranilate. Homosalate is available commercially from Merck under the
tradename Eusolex HMS and menthyl anthranilate is commercially available
from Haarmann & Reimer under the tradename Heliopan. If present, the
Homosalate should be found at no more than about 15% by weight of the
total composition.

[0125] Various amino benzoic acid derivatives are suitable UVB absorbers
including those having the general formula:

##STR00020##

wherein R.sub.1, R.sub.2, and R.sub.3 are each independently H,
C.sub.1-20 straight or branched chain alkyl which may be substituted with
one or more hydroxy groups. Particularly preferred is wherein R.sub.1 is
H or C.sub.1-8 straight or branched alkyl, and R.sub.2 and R.sub.3 are H,
or C.sub.1-8 straight or branched chain alkyl. Particularly preferred are
PABA, ethyl hexyl dimethyl PABA (Padimate O), ethyldihydroxypropyl PABA,
and the like. If present Padimate O should be found at no more than about
8% by weight of the total composition.

[0126] Salicylate derivatives are also acceptable UVB absorbers. Such
compounds have the general formula:

##STR00021##

wherein R is a straight or branched chain alkyl, including derivatives of
the above compound formed from mono-, di-, or triethanolamines.
Particular preferred are octyl salicylate, TEA-salicylate,
DEA-salicylate, and mixtures thereof. Generally, the amount of the UVB
chemical sunscreen present may range from about 0.001-45%, preferably
0.005-40%, more preferably about 0.01-35% by weight of the total
composition.

[0127] A particularly preferred sunscreen agent is including
bisiminomethylguaiacol manganese chloride, in view of its cationic
charge.

[0128] If desired, the compositions of the invention may be formulated to
have a certain SPF (sun protective factor) values ranging from about
1-50, preferably about 2-45, most preferably about 5-30. Calculation of
SPF values is well known in the art.

[0129] The compositions of the invention may contain particulate materials
in addition to the optically reflective materials, including other
pigments, inert particulates, or mixtures thereof. Suggested ranges for
all particulate materials is from about 0.01-75%, preferably about
0.5-70%, more preferably about 0.1-65% by weight of the total
composition. In the case where the composition may comprise mixtures of
pigments and powders, suitable ranges include about 0.01-75% pigment and
0.1-75% powder, such weights by weight of the total composition.

[0133] The compositions of the invention may contain vitamins and/or
coenzymes, as well as antioxidants. If so, 0.001-10%, preferably 0.01-8%,
more preferably 0.05-5% by weight of the total composition is suggested.
Suitable vitamins include ascorbic acid and derivatives thereof such as
ascorbyl palmitate, tetrahexydecyl ascorbate, and so on; the B vitamins
such as thiamine, riboflavin, pyridoxin, and so on, as well as coenzymes
such as thiamine pyrophoshate, flavin adenin dinucleotide, folic acid,
pyridoxal phosphate, tetrahydrofolic acid, and so on. Also Vitamin A and
derivatives thereof are suitable. Examples are retinyl palmitate,
retinol. retinoic acid, as well as Vitamin A in the form of beta
carotene. Also suitable is Vitamin E and derivatives thereof such as
Vitamin E acetate, nicotinate, or other esters thereof. In addition,
Vitamins D and K are suitable.

[0134] Suitable antioxidants are ingredients which assist in preventing or
retarding spoilage. Examples of antioxidants suitable for use in the
compositions of the invention are potassium sulfite, sodium bisulfite,
sodium erythrobate, sodium metabisulfite, sodium sulfite, propyl gallate,
cysteine hydrochloride, butylated hydroxytoluene, butylated
hydroxyanisole, and so on.

[0136] The invention further comprises treating skin for improvement by
applying to the skin the compositions of the invention. The systems may
be applied in the forms mentioned herein, as part of skin care regimens.
For example, the system may be applied to the skin alone, or incorporated
into a day cream. The systems may be applied after cleansing the skin.
The systems may be applied to the skin under or over skin care products,
such as foundations or other color cosmetics or incorporated into such
skin care products.

[0137] Dry, treated particulates of the present invention may be applied
to clean, dry eyelashes after application of a coating of conventional
mascara, or between applications of conventional mascara. Formulations
according to the present invention may take a variety of forms. The
formulation may be a mascara composition which is similar to a
conventional mascara but which contains fibers treated according to the
present invention; that is, fibers provided with a cationic coating, and,
optionally, with a further coating containing film former and, with or
without one or more intermediate coatings between the initial cationic
coating and the film former. One or more coats of the mascara containing
fibers treated according to the invention may be applied to the eyelashes
to increase volume and length of the lashes, depending on the user's
needs. The formulation also may take the form of a pigmented or
unpigmented waxy- or gel-based composition containing the
cationically-coated fibers in a hydrophilic carrier, such as water and
alcohol. The latter formulation may be applied to clean, dry eyelashes to
provide enhanced volume and length, optionally followed by the
application of a conventional mascara. Or, the waxy- or gel-based formula
may be applied between coats of conventional mascara. Formulations
according to the present invention will not only enhance the volume and
length of eyelashes of the user, but, due to the presence of the charged
fibers, will result in wear which is superior to that achievable with
fiber-containing conventional products. It will be apparent to those of
skill in the art that the formulations of the invention also may be used
as a brow or hair filler.

[0138] The following examples further illustrate various specific
embodiments of the present invention, without limiting the broad scope
thereof.

EXAMPLES

Example 1

Preparation of Treated Fibers

Procedure:

[0139] 1. 150 gms. of Splash Fiber II 7T 1 mm fibers (available from
Kobo Products, Inc.) were introduced into the fluid bed of a
microfluidizer (Glatt Air Techniques, model no. GPCG-1). [0140] 2. Fibers
were fluidized at 25% flap with the temperature set to 60.degree. C.
[0141] 3. 150 gms. of a cationically charged solution containing 15 wt. %
polyquaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was top
sprayed from the lower port of the fluidizer at 2.5 bar atomizing air
pressure & 30 rpm pump speed over a period of about 19 minutes. To
minimize clumping of fibers, spraying was paused twice to allow the
fibers to dry and start flowing again. [0142] 4. Fibers were allowed to
dry for 35 min with 60.degree. C. inlet air. Levelling off of the product
temperature for 10 minutes, followed by increasing temperature, signalled
that the moisture had been removed. [0143] 5. 60 gms. of a film-former
solution containing hydrophobic silicones as follows: 52.19 wt. % methyl
trimethicone, 35.4 wt. % trimethylsilicate and 12.41 wt. % dimethicone
was top sprayed, from the lower port of the at 2.5 bar atomizing air
pressure & 30 rpm pump speed over a period of about 7 minutes. [0144] 6.
Fibers were allowed to dry for 15 minutes with 60.degree. C. inlet air.
[0145] 7. Confocal analysis confirmed that the fibers were completed
coated.

Example 2

Attraction of Hair to Treated Fibers

Procedure:

[0145] [0146] 1. First and second hair swatches, weighing 1.36 gms. and
1.68 gms., respectively were introduced into separate vessels containing
either control fibers ((nylon-6 (and) black iron oxide (and) silica,
available as SPLASH FIBER II 7T-2MM, from Kobo Products, Inc.) or coated
fibers prepared as in Example 1. [0147] 2. After about 2 minutes, each of
the hair swatches was removed from the respective vessels and re-weighed.

Result:

[0148] It was observed that the swatch introduced into the vessel
containing the control fibers still weighed 1.36 gms., while the hair
swatch introduced into the vessel containing the treated fibers weighed
1.70 gms. indicating that the hair swatch attracted 0.02 gms of treated
fibers.

Example 3

Preparation of Treated Fibers

Procedure:

[0149] 1. 300 gms. of Silk Cotton PW fibers (available from Kobo
Products, Inc.) were introduced into the fluid bed fo a microfluidizer.
[0150] 2. Fibers were fluidized at 25% flap with the temperature set to
20.degree. C. [0151] 3. 300 g of a cationically charged solution
containing 15 wt. % poly quaternium-6, 70 wt. % water and 15 wt. %
denatured alcohol was top sprayed from the lower port of the fluidizer at
2.5 bar atomizing air pressure & 30 rpm pump speed over a continuous
period of about 40 minutes. [0152] 4. Fibers were permitted to dry for 50
minutes with 60.degree. C. inlet air. Levelling off of the product
temperature for 10 minutes, followed by increasing temperature, signalled
that the moisture had been removed. [0153] 5. 300 gms. of a dispersion of
hydrophilic film-former, polyurethane-35 in water (41 wt.% polyurethane
in water, available as Baycusan C 1004 from Covestro) was top sprayed,
from the lower port of the fluidizer, at 2.5 bar atomizing air pressure &
30 rpm pump speed over a period of 38 minutes. [0154] 6. Fibers were
dried for 50 minutes with 60.degree. C. inlet air. [0155] 7. Confocal
analysis confirmed that the fibers were completed coated.

Example 4

Dispersibility of Fibers in Water

Procedure:

[0155] [0156] 1. 5 gms of each of the treated Silk Cotton PW fibers of
Example 3, Silk Cotton PW fibers coated only with the cationically
charged material used in Example 3, and untreated control Silk Cotton PW
fibers, were dispersed in separate vessels, each containing 50 ml water.
[0157] 2. After 10 minutes, it was observed that the twice-coated Silk
Cotton PW fibers presented as two phases; the hydrophobic fibers not
being water-dispersible, floated to the top of the water. The fibers
receiving only the cationically charged coating were partially
dispersible, some fibers settling to the bottom of the vessel. The
control fibers, absorbing water, settled to the bottom of the vessel.

Example 5

Preparation of Treated Fibers

Procedure:

[0157] [0158] 1. 200 gms. of Splash Fiber II 7T 1 mm were introduced
into the fluid bed of a fluidizer. [0159] 2. Fibers were fluidized at 25%
flap with the temperature set to 20.degree. C. [0160] 3. 100 gms. of a
cationically charged solution containing 15 wt. % poly quaternium-6, 70
wt. % water and 15 wt. % denatured alcohol was top sprayed from the lower
port of the fluidizer at 2.5 bar atomizing air pressure & 30 rpm pump
speed until fibers were observed to clump and fluidization was lost.
[0161] 4. Fibers were dried for 15 minutes with inlet air at 60.degree.
C. to drive off sufficient moisture until fluidization resumed. Inlet air
remained on for the remainder of the process. [0162] 5. An additional 100
gms. of the cationically charged solution containing 15 wt. % poly
quaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was top
sprayed from the lower port of the fluidizer at 2.5 bar atomizing air
pressure & 30 rpm pump speed until fibers were observed to clump and
fluization was lost. [0163] 6. The fibers then were dried at 60.degree.
C. with inlet air for 50 minutes. [0164] 7. 200 gms. of of a dispersion
of hydrophilic film-former, polyurethane-35, in water (available from
Covestro as Baycusan C 1004--was top sprayed, from the lower port of the
fluidizer, at 2.5 bar atomizing air pressure & 30 rpm pump speed over a
period of 20 minutes with no significant clumping observed. [0165] 8.
Fibers were dried at 60.degree. C. for 50 minutes. [0166] 9. Confocal
analysis confirmed that the fibers were completed coated.

Example 6

Preparation of Treated Fibers

Procedure:

[0166] [0167] 1. 100 gms of NFBL-10D-1R ((nylon-6 (and) iron oxides
(and) triethoxycapryl silane (and) silica, available from Kobo Products,
Inc.)) was introduced into the bed of a fluidizer. [0168] 2. Fibers were
fluidized at 25% flap with the temperature set to 20.degree. C. [0169] 3.
100 gms. of a cationically charged solution containing 15 wt. % poly
quaternium-6, 70 wt. % water and 15 wt. % denatured alcohol was top
sprayed from the lower port of the fluidizer at 2.5 bar atomizing air
pressure & 10 rpm pump speed until fibers were observed to clump and
fluidization was lost. [0170] 4. Fibers were dried for 15 minutes with
inlet air at 60.degree. C. to drive off sufficient moisture until
fluidization resumed. Inlet air remained on for the remainder of the
process. [0171] 5. 100 gms. of a film-former solution containing a
mixture of 59.46 wt. % trisiloxane, 20.27 wt. % dimethicone and 20.27 wt.
% trimethylsiloxysilicate was top sprayed, from the lower port of the
fluidizer, at 2.5 bar atomizing air pressure & 5 rpm pump speed over a
period of 20 minutes with no significant clumping observed. [0172] 6.
Fibers were dried at 60.degree. C. for 50 minutes. [0173] 7. Confocal
analysis confirmed that the fibers were completed coated. The zeta
potential (measured by Brookhaven Instruments, model NanoBrook Omni
28001, spectrophotometer) of the treated fibers was determined to be 143
mV.

[0176] Example 8 was repeated except that the cationically charged fibers
were sprayed with 7.5 wt. % of a film former solution containing 59.46
wt. % trisiloxane, 20.27 wt. % dimethicone and 20.27 wt. %
trimethylsiloxysilicate. The zeta portential of the treated fibers was
determined to be 59 mV.

[0178] The process of Example 6 was repeated except that an intermediate
coating of 0.1 weight percent aqueous solution of grapeseed extract was
sprayed on the cationically coated fibers prior to coating with the film
former solution.

[0182] 2. To evaluate the uniformity of the coating on the fibers, 0.02 gm
samples of the coated fibers were examined under a confocal microscope
with transmission light (about 300 nm) and laser light (about 488 nm),
respectively. Under laser light, it was observed that the entire
peripheral surfaces of every fiber fluoresced indicating that each fiber
was fully encapsulated with the cationic coating. No fluorescence was
observed under transmission light.

[0185] 3. To evaluate the uniformity of the cationic coating on the
fibers, and to ascertain whether the silicone blend would permit or block
illumination of the fluorescein, 0.02 gm samples of the coated fibers
were examined under a confocal microscope with transmission light and
with laser light, respectively. It was observed that the entire
peripheral surface of each fiber fluoresced under the laser light
indicating that the cationic coating remained uniform.

C.

[0186] 1. Step A1 was repeated.

[0187] 2. The cationically coated fibers were washed 20 times, for 30
minutes each time, in water at 3000 rpm in a centrifuge and then dried in
an incubator overnight at 50.degree. C.

[0188] 3. To evaluate the uniformity of the cationic coating on the
fibers, 0.02 gm samples of the cationically coated fibers were examined
under a confocal microscope with transmission light and with laser light,
respectively. Under laser light, it was confirmed that all of the
cationic coating had been removed from the fibers, as observed by the
lack of fluorescence.

D.

[0189] 1. Steps C 1 and 2 were repeated except that the cationically
coated fibers were washed only once, and dried.

[0191] 3. The fibers of step 2 were then washed 20 times, and then dried,
as described above.

[0192] 4. To evaluate the uniformity of the cationic coating on the
fibers, 0.02 gm samples of the cationically coated fibers were examined
under a confocal microscope with transmission light and with laser light,
respectively. The observation of the illumination of the entire periphery
of each fiber under laser light confirmed that each fiber remained fully
coated with the cationic material. The silicone coating not only sealed
the cationic coating to the fibers but also rendered the fibers
water-resistant.

[0193] 1. 1-2 grams of virgin fibers (nylon-6: NFCB-10D-1R 1 mm--nylon
fiber/FDA certified carbon black/10 denier/1 mm/round, available from
Daito Kasei Kogyo Co. Ltd.) were loosely packed, using a spatula, into a
tube equipped with a wiper, and the tube was secured with a cap fitted
with a brush. 1-2 grams of cationically-charged fibers (nylon-6:
NFCB-10D-1R 1 mm--nylon fiber/FDA certified carbon black/10 denier/1
mm/round, obtained from Daito Kasei Kogyo Co. Ltd., subsequently
encapsulated with polyquaternium-6, and then further treated with a
hydrophilic film-former coating of dimethicone and
trimethylsiloxysilicate/polyglyceryl-3 siloxane dimethicone in
trisiloxane were loosely packed, using a spatula, into a separate tube
equipped with a wiper, and the tube was secured with a cap fitted with a
brush.

[0194] 2. The respective caps were then removed from each of the tubes,
the brush in each tube, loaded with fibers, being withdrawn through the
wiper, over separate blank sheets of white paper.

[0195] 3. FIG. 1 shows fibers scattred over the initially blank white
paper. Virgin fibers carry no charge of their own; however, as the brush
loaded with fibers was withdrawn from the tube, through the wiper, the
friction produced by the brush moving through the wiper caused the brush
to be statically (i.e., relatively negatively) charged. The previously
uncharged virgin fibers captured in the bristles of the brush also became
negatively charged by attracting negative charges from the atmosphere.
The statically charged fibers repelled one another as well as the brush.
It was further observed that the brush could not be fully inserted back
into the tube after being withdrawn. Prior to the brush being withdrawn,
the fibers were loosely entangled about one another around the brush in
the tube. Inserting the negatively charged brush back into the tube
through the wiper caused the entangled fibers to be compacted in the
bottom of the tube so that the brush could not be reloaded with fibers.

[0196] 4. FIG. 2 depicts a blank sheet of paper, since the film-former
coated, cationically charged fibers according to the invention, did not
scatter from the brush onto the paper as the brush was withdrawn from the
tube, but remained entrapped in the bristles of the brush. Although the
friction caused by the brush moving through the wiper caused the brush to
be statically (i.e., relatively negative) charged, and although the
film-former coated, cationically-charged fibers according to the
invention also picked up negative charges from the atmosphere, the
positive and negative charges on the fibers briefly canceled each other
out. As a result, the fibers did not repel one another. As the static
charge on the fibers dissipated, the positively charged fibers adhered to
the negatively charged brush. The brush was easily re-inserted into the
tube because the coated, cationically charged fibers in the tube did not
agglomerate or compact.

[0198] 2. A panelist applied a first coat of a commercial (non-waterproof)
mascara to the lashes of both eyes.

[0199] 3. The panelist immediately thereafter applied the virgin fibers to
the mascara-coated lashes of the right eye, using the brush applicator,
while the mascara was still tacky. The panelist then applied the film
former-coated, cationically-charged fibers, using the brush applicator,
onto the lashes of the left eye while the mascara was still tacky. The
panelist noted that the virgin fibers were difficult to apply and began
to fall to the cheek during application. As shown in FIG. 3, while some
fibers adhered to the lashes, fibers also flew about and about 90 fibers
were counted on the skin of the right cheek and the right side of the
nose. On the other hand, the coated, cationically-charged fibers were
smoothly and easily applied, and adhered well to the lashes. As discussed
above in Example 16, while the virgin fibers carried static charges which
caused them to repel one another and neither adhere well to the brush or
to the lashes, the positively charged fibers of the invention adhered to
the brush carrying the static (i.e., negative) charges and to the
negatively charges lashes.

[0200] 4. Any fallen fibers were then wiped clean from both undereye areas
including the cheek and the nose.

[0201] 5. One hour after the initial applications of fibers to the
mascara-coated lashes, about 30 virgin fibers were observed on the skin
of the cheek under the right eye, as shown in FIG. 4. Additionally, eye
irritation was reported. In contrast, the film-former coated,
cationically-charged fibers of the invention remained adhered to the
lashes. Only two fibers were observed to have fallen on the undereye area
of the left eye, as shown in FIG. 5.

[0202] Although the invention has been variously disclosed herein with
reference to illustrative embodiments and features, it will be
appreciated that the embodiments and features described hereinabove are
not intended to limit the scope of the invention, and that other
variations, modifications and other embodiments will suggest themselves
to those of ordinary skill in the art. The invention therefore is to be
broadly construed, consistent with the claims hereafter set forth.